4.7 Article

Rational design and synthesis of hollow Co3O4@Fe2O3 core-shell nanostructure for the catalytic degradation of norfloxacin by coupling with peroxymonosulfate

Journal

CHEMICAL ENGINEERING JOURNAL
Volume 359, Issue -, Pages 373-384

Publisher

ELSEVIER SCIENCE SA
DOI: 10.1016/j.cej.2018.11.120

Keywords

MOFs; Sulfate radicals; Norfloxacin; AOPs; EPR

Funding

  1. National Natural Science Foundation of China [51608274]
  2. National Science and Technology Major Project [2017ZX07204001-06]
  3. Research Foundation of Jiangsu Environmental Protection Department [2017002]
  4. Fundamental Research Funds for the Central Universities [KYZ 201619, KJQN 201749]

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Rational design and synthesis of efficient catalyst for the generation of sulfate radicals (SO4 center dot-) through heterogeneous approach is highly desirable. In the present study, a magnetic cobalt-based catalyst, Co3O4@Fe2O3 was successfully synthesized by using metal-organic frameworks (MOFs) as a template. A hollow core-shell structure possessing moderate specific surface area (22.8 m(2) g(-1)) and pore volume (0.18 cm(3) g(-1)) was obtained. The catalyst performed high efficiency for the degradation of norfloxacin (NOR) by coupling with peroxymonosulfate (PMS). And the process was kinetically favorable in neutral (0.43 min(-1) at pH of 7.5) and weak acidic/basic conditions, whilst significantly inhibited at acidic condition (0.12 min(-1) at pH of 4.5). Catalyst loading showed a more remarkable effect on the degradation process than PMS dose. Interestingly, chloride, phosphate and bicarbonate ions clearly promoted the degradation process while humic acid showed a detrimental effect. Cl-2/HOCl oxidation system was demonstrated when massive Cl- was added into the reaction system. As evidenced by electron paramagnetic resonance (EPR) analysis, both hydroxyl and sulfate radicals contributed to the degradation and the latter one played a crucial role. Eventually, degradation pathway was tentatively proposed based on the HPLC-ESI-MS/MS analysis of the detected intermediates. This study would be very meaningful to promote the applications of sulfate radical based advanced oxidation processes (SR-AOPs) for the environmental remediation.

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